Herein,a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution(S_(N)Ar) using TMSCN as a cheap cyanide source under mild conditions has been presented.This transformat...Herein,a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution(S_(N)Ar) using TMSCN as a cheap cyanide source under mild conditions has been presented.This transformation utilizes commercially available reagents,cheap electrodes,and simple equipment.Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope,excellent functional group tolerance,and selective C-O bond cleavage.Furthermore,late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy.Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation,and undergoing the followed S_(N)Ar process.展开更多
A general strategy forβ-selective silylcarbonylation of styrenes with CO_(2) via electrochemical reduction has been reported.A series of styrenes have been simultaneously introduced with silyl and carboxyl groups,and...A general strategy forβ-selective silylcarbonylation of styrenes with CO_(2) via electrochemical reduction has been reported.A series of styrenes have been simultaneously introduced with silyl and carboxyl groups,and these groups have been further converted to high-value functional groups.Detailed mechanistic experiments have proven that the single-electron reduction of CO_(2) is the key to this unique regioselectivity.展开更多
Herein,an electrochemically driven catalyst-free nucleophilic aromatic substitution(S_(N)Ar)of electron-rich fluoroarenes with carboxylic acids as weak nucleophiles under mild conditions was reported.A series of highl...Herein,an electrochemically driven catalyst-free nucleophilic aromatic substitution(S_(N)Ar)of electron-rich fluoroarenes with carboxylic acids as weak nucleophiles under mild conditions was reported.A series of highly valuable ester derivatives were obtained in a direct and rapid way.This transformation features commercially available reagents and an exceptionally broad substrate scope with good functional group tolerance,using cheap and abundant electrodes and completed within a short reaction time.Gram-scale synthesis and complex biorelevant compounds ligation further highlighted the potential utility of the methodology.The mechanistic investigations and density functional theory(DFT)calculations verified the feasibility of the proposed pathway of this transformation.展开更多
基金Financial support from National Key R&D Program of China(No.2023YFA1507203)National Natural Science Foundation of China(Nos.22371149,22188101)+2 种基金the Fundamental Research Funds for the Central Universities(No.63224098)Frontiers Science Center for New Organic Matter,Nankai University(No.63181206)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Herein,a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution(S_(N)Ar) using TMSCN as a cheap cyanide source under mild conditions has been presented.This transformation utilizes commercially available reagents,cheap electrodes,and simple equipment.Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope,excellent functional group tolerance,and selective C-O bond cleavage.Furthermore,late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy.Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation,and undergoing the followed S_(N)Ar process.
基金supported by the National Key R&D Program of China(2023YFA1507203)the National Natural Science Foundation of China(22371149,22301144,and 22188101)+3 种基金the Natural Science Foundation of Tianjin(24JCJQJC00210)the Fundamental Research Funds for the Central Universities(63223015)Frontiers Science Center for New Organic Matter,Nankai University(63181206)Nankai University are gratefully acknowledged.
文摘A general strategy forβ-selective silylcarbonylation of styrenes with CO_(2) via electrochemical reduction has been reported.A series of styrenes have been simultaneously introduced with silyl and carboxyl groups,and these groups have been further converted to high-value functional groups.Detailed mechanistic experiments have proven that the single-electron reduction of CO_(2) is the key to this unique regioselectivity.
基金Financial support from National Key R&D Program of China(2022YFA1503200)National Natural Science Foundation of China(Grant No.22371149,22188101)+2 种基金the Fundamental Research Funds for the Central Universities(No.63223015)Frontiers Science Center for New Organic Matter,Nankai University(Grant No.63181206)Nankai University are gratefully acknowledged.
文摘Herein,an electrochemically driven catalyst-free nucleophilic aromatic substitution(S_(N)Ar)of electron-rich fluoroarenes with carboxylic acids as weak nucleophiles under mild conditions was reported.A series of highly valuable ester derivatives were obtained in a direct and rapid way.This transformation features commercially available reagents and an exceptionally broad substrate scope with good functional group tolerance,using cheap and abundant electrodes and completed within a short reaction time.Gram-scale synthesis and complex biorelevant compounds ligation further highlighted the potential utility of the methodology.The mechanistic investigations and density functional theory(DFT)calculations verified the feasibility of the proposed pathway of this transformation.
